Water-insoluble styryl dyestuffs



a r e United States Patent 1 2,936,319 WATER-INSOLUBLE STYRYL DYESTUFFS Ernest Merian, Bottmingen, Bruno J. R. Nicolaus, Basel,

and Otto Senn, Arlesheim, Switzerland, assignors to Sandoz A.G., Basel, Switzerland No Drawing. Application July 12, 1957 Serial No. 671,419 Claims priority, application Switzerland August 3, 1956 7 Claims. (Cl. 260-465) The present invention relates to new water-insoluble styryl dyestuffs which possess the general formula X R1-OHOH I SOs-and R, denotes chlorine, bromine, or the R COO radical in which R stands for a methyl, chloromethyl, ethyl, n-propyl, isopropyl, methoxymethyl or ethoxymethyl radical,

R an alkyl radical with 1 to 4 carbon atoms or, when R,

stands for the R --COO radical, also the X a methyl or ethyl radical,

Y hydrogen, a methyl, ethyl, methoxy or ethoxy radical, Z hydrogen or a methyl radical, and

m the number 1 or 2.

The process for the production of the new Water-insoluble styryl dyestuffs consists in condensing 1 or 2 mols of an aldehyde free from water-solubilizing groups and having the formula wherein R R X, Y and Z possess the aforementioned meanings with 1 mol of an active methylene compound of the formula wherein m represents the figure 1 or 2; The process is a further feature of the invention.

The reaction of the aldehyde with the active methylene compound is performed advantageously by causing the aldehyde to act upon the said compound at elevated temperature in homogeneous solution in a suitable solvent and in presence of a small quantity of a basic substance, e.g. ammonia, dimethylamine, diethylamine or piperidine.

It is also possible to heat a mixture of the aboveice mentioned reactants in presence of glacial acetic acid or another organic acid plus a proton acceptor such as ammonia, diethylamine, dimethylamine or piperidine in a hydrocarbon like benzene, toluene, xylene, or chloroform or carbon tetrachloride, the organic solvent acting as a recycling agent. The Water of reaction is continuously drained off so that there is a constant shift in the equilibrium position to the side of the condensation product.

Condensation can also be conducted by saturating a homogeneous solution of the two reactants in a suitable solvent with dry hydrogen chloride. This procedure gives rise to a hydrogen chloride addition product, which upon distilling or heating with tertiary bases such as dimethylaniline or diethylaniline, splits off the hydrogen chloride to yield the desired ethylidene compound.

Finally, condensation can be carried out by melting together the reactants and a basic catalyst such at ammonia, dimethylamine, diethylamine, piperidine, ammonium acetate or piperidine acetate in the absence of solvent.

The dyestufis are isolated by one of the common basic operations, e.g. filtration, evaporation of the solvent or precipitation from the solvent with a suitable precipitating agent.

The new styryl dyestuffs possess a clearly defined absorption band in the visible region and are characterized by an excellent color yield and also by their brilliancy of shade.

They may be applied singly or in combination with other dyestuffs of the same composition for the mass pigmentation of oils, lacquer media, moulding resins and other plastics, and solutions of textile fibers which are subsequently extruded as filament.

One field of application, for example, is the mass or dope dyeing of secondary cellulose acetate and triacetate in greenish yellow to neutral yellow shades. The spundyed filament exhibits very good fastness to light, washing, Water, perspiration, cross-dyeing, crocking, ironing, sublimation, chlorine in alkaline medium, hydrosulfite, gas fumes, and oxalic acid, and withstand dry cleaning and peroxide bleaching.

Furthermore a certain number of the new dyestufis are suitable for dyeing synthetic fibers in the melt prior to spinning, a process employed for the synthetic polyamide and polyester fibers. In this connection it may be noted that almost all of the azo dyestuffs are destroyed under the temperature conditions obtaining in this process.

In the examples which follow all the specified weights and percentages are by weight. The temperatures are in degrees centigrade and the melting points are uncorrected.

EXAMPLE 1 33.5 parts of l-(N-dipropionyloxyethyl)-amino 3- methyl-4-benzaldehyde with' 19.5 parts of (4-methylphenyl-l-sulfonyl)-acetonitrile and 1 part of piperidine in 50 parts of methyl alcohol are heated to the boil with reflux.

At this point the mass takes on a deep yellow color. After some time it is cooled to 0, upon which the new styryl dyestuff crystallizes out in beautiful yellow needles. It is filtered ofi, Washed with cold alcohol and dried. The dyestufi is very soluble in acetone and melts at 88. Applied in spinning solutions of secondary cellulose acetate, it yields brilliant greenish yellow shades which have very good fastness properties.

parts of secondary cellulose acetate are dissolved in 300 parts of a mixture of acetone and methanol in the ratio 93:7. The mass is mixed for a short time and left overnight to swell. 0.5 part of the styryl dyestufi I The aldehyde used as starting material is produced in the following way:

44 parts of N,N-dimethylforinamide, 120 parts of phosphorus oxychloride, 30 parts of chlorobenzene and 30.7 parts. of l-(Ndipropionyloxyethyl)-arnino-3-methylbenzene are stirred for 12 hours at 60. As soon as the parts of the .dyestufi obtained as described in the foregoing paragraph and 600 parts of xylene is extruded through the 0.5 diameter orifice of a spinning nozzle into mixtures of butyl alcohol and butyl phthalate. The greenish yellow filaments formed by precipitation are washed in petroleum ether and dried in a warm atmosphere.

The mixture of l-(N-ethyl-N-chloroethyl)-arnino-3- methyl-4-benzaldehyde and l-(N,N-diethyl)-amino-3- methyl-4-benzaldehyde used as starting product is produced by treating 180 parts of a technical mixture of 1- (N-ethyl-N-hydroxyethyl)-amino-3-"nethylbenzene and 1- (N,N-diethyl)-amino-3-methylbenzene with 460 parts of phosphorus oxychloride and 270 parts of N-methyl-N- reaction is completed the reaction mass is poured onto formyl-aminobcnzene for 16 hours at 45. The crude a mixture of 300 parts of ice and 300 parts of water with aldehyde mixture thus obtained melts at 4l-47". thorough stirring. The resultant suspension is adjusted 1 AMPLE 4 to pH.6 by the addition of a 5% sodium hydroxide solution. After some time the chlorobenzene layer is P P 0f the Parts of the aldehyde separated and is boiled down in vacuo. The aldehyde flllxture used 111 P F 3 y 225 Parts 0f P is a light-colored oil which congeals in a short time. t y y 9 Y l/ the EXAMPLE 2 styryl dyestufi, which is obtained in a purer form, melts a I a f 'When the same amount of the aldehyde employed in t 180 upon'recn st lhzauon mm ethanol Example 1 is condensed with parts of (3.4-dichloro- 25 EXAMPLE 5 l -P f i f yenow dyestufi whose 22.5 parts of pure l-(N-ethyl-N-chloroethyl)-aniino-3- memng P 13 125 r15 obtfimefl" I methyl-4-benzaldehyde are inixed with 20 parts of 4- 200 pailts of f i 5 Parts Of the methylbenzene-l-sulfonylacetonitrile at 50-60 to give Stuff Pbtamed as flxainple Parts of methylene a homogeneous paste. 1 part of piperidine is added to chloride and 4-9 pa -ts o ethanol are compounded to a 30 the paste and the temperature of the mass is raised to homogeneous mass. iliis is pumped into the spinning 0 with constant stirring After some time thermacb P a Spun hy the iiorniai method :Ihesplin fila tion is completed. The deep yellow colored mass is 18 dyed to a P lght greemfh yellow mane Whlc possesses poured While still hot onto a sheet of stainless steel and excfinent fasfiness Propemesallowed to congeal. The crude styryl dyestuff is then The (3.4dichlorophenyl-l-sulfonyl)-acetonitiile is new finey ground It melts at 1674730 and is readily and is obtained in the following manner: soluble in acetone; 23.3 parts 01: sodium 3.4-dichlorohenzene-l-sulfinate, 1 Part of the dyestuff obtainable according to Example 9 Parts of 10 Parts ofFnlomacetaPnde are 5 and 150 parts of polyvinyl chloride are dissolved in 849 stirred for hOLlllll at The reaction product is filtered parts of cyclohexanone at The hot Solution is sub off and (mad wroughly- It 181mm f Into 60 Parts 0 sequently extruded into a bath of 500 parts of cyclohexaof phosphorus oxychloride and tne react on mass stirred none and 9500 parts of zethylhexanone, where it is for 3 hours on completlon of me macho? cipitated to form a green-yellow filament which is reeled, loaded upon ice water, filtered off, and washed until the dried under tension and orientated filtrate re acts neutral. The dried crude product melts at In the following Table 1 valuable styryl dyestuffs are 102-103 45 described which can be produced by the process disclosed EXAMPLE 3 in the foregoing. They correspond to the general formula 22.5 parts of a technical mixture of l-(N-ethyl-N- CH3 chloroethyl) amino 3 methyl 4 benzaldehyde and 1- Ri-CH-GH2 SOi.-aryi (N,N-diethyl)amino-3-methyl-4-benzaldehyde together with 20 parts of 4-inethylbenzene-l-sulfonylacetonitrile 0 and 1 part of piperidine in 30 parts of ethanol are heated (IV) to the boil with reflux. The mass is deep yellow in color Th6 meijmmgs of 1 2 and n are given Under th at this stage. It is maintained at the boil for 24 hours pp p headmgs- A further 0011mm C0 and then allowed to cool whereupon the new styryl dyetalYiS h meltlng POlIltS 0f the new y y Y h stuff crystallizes out. it is filtered on, washed with Water 55 penultimate and d columns respectlvely glve Informand dried. In the crude state it melts at 168-173"; it is t on 011 the Solubility of the dyestuffs in acetone, exreadily soluble in acetone. pressed in grams per liter, and the shade of the spun- A solution composed of 400 parts of polyethylene, 4 dyed cellulose acetate filament.

Table 1 Solubility Shadein M.P., in Spun- Ex. N 0. R R1 aryl m degrees acetone, Dyed g. per 1. Cellulose Acetate 6 chlorine-.. ethyl phenyl 1 173 30 greenish yellow. 7 do .do 5,6,7,8-tetrahy- 1 136 Do.

dronaphthyl-2. 8 d0 do 2-methyl-5-isopro- 1 113 100 Do pylphenyl-l. 9 do .do 3,4-dichlorophenyl-l.-- 1 161 30 Do acetoxy ethyl 4-methylphenyl-1 1 175 66 Do propionoxyethyl naphthy1-2 1 126 100 Do 4,4-diphenyl 2 136 44 Do naphthy1-1,5 2 126 200 Do naphthyl-2,6 2 246 10 Do in columns (I) to (1H) and by'the shade or spun-dyed cellulose acetate in column (IV).

esem -do isopropyL- do chloroethyl ..d

do 4-tert.butylphenyldo 4-chlorophenyl-L. do

8 Table 4 aryl D chlorine.

BA-dimethylphenyl-L- 4-ethylphenyl-l Do. 4is0pr0pylphe11yl-1. 4-tert. but ylpheuyl-l. 4-chlorophenyl-l..- -fiuorophenyl-l. 4brornophenyl-l uaphthyl-Z 5.6. 7.8-tetrahydronaphthyl-Z.

naphthyl-Z V phenyl 4-methy1phenyl-1 3.4dimethylphenyl-l.- eethylphenyl-l 4-isopropylphenyl-l- 4-tert. butylphenyl-L.

In Table 5 a few Water-insoluble monoazo dyestufis "are' described. They correspond to the formula Table 4 sets forth styryl dyestuffs which correspond to the formula CH=C cellulose acetate in column (V).

SO,-aryl CH2 40 e v'--CH':=OI{: I so,- -om V v /N- 013:0 7 l w'-C'Hz-CHn l ON Y' v-111 and are characterized by the symbols v, w and Y in 5 columns '(I) to (111) and by the shade of spunedyed l cellulose acetate in column (1V);

. Table 5 V V (I Yl Shade of Spam. Ex. No. v w Y Dyed:

. Cellulose Acetate 184..-- chlorine-.-" hydroge methyl-.-- greenish- --yel1ow.

' Zparts of the dyestuif produced as described idExample 7, 280 parts of post-chlorinated polyvinyl chloride and 10 parts of diearylsulfide are dissolved in 708 parts "of acetone at 40. The resultant mass is pumped into 115a spinning pot and extruded in the normal manner,

' greenish yellow.

EXAMPLE 193 Anmixture of 1 part of the dyestnfi obtained in ac- 7 cordance with Example 9, 199 parts of a copolymer the fila-n ent being precipitated with water. Ityis then 0.. orientated and dried at 40 to The shade is a ments or bristles-are obtained. Polystyrene can be solution-dyed with this d'y'estflff in a similar manner.

Formulae of representative dyestufls of the foregoing examples are t 9 composed-of 60.1% of vinyl chloride and 39.9% parts of acrylonitrile, and 800 parts. of acetone are mixed together for 4 hours at 50. A homogeneous yellow solution is obtained which is filtered and spun into filament, using water as precipitant. The filament is orien- EXAMPLE 1 tated and seat-set in boiling water. The finished filament is of yellow shade and has good fastness properties. cHrOflrcOo-CHx-cgl /S0g -CH| EXAMPLE 194 N-CH=O\ 165 parts of polyacrylonitrile and 1 part of the dye- GHrCHPCOO'CHPCFl UN stufi obtained according to Example .11 are dissolved EXAMPLE 2 CHe-CHr-C O O-GHg-Cfi EXAMPLE 3 at 100 in 834 parts of dimethylformamide. The mass so formed is extruded from a spinnerette using the normal procedure for viscose rayon. The resulting filament is precipitated with water and orientated in a hot water bath at 90. The spun-dyed filament is of bright yellow shade and possesses good fastness properties.

EXAMPLE 195 1 part of the dyestufi obtainable as specified in Example 12 and 179 parts of polyacrylonitrile are dissolved in 820 parts of dimethylformamide at 100. These components form a paste which is extruded from a spinnerette into a bath of glycerol at 140. The filament is reeled and orientated, washed with water to clear it of glycerol, and CHVCH2 then dried. Greenish yellow shades of good all-round fastness are obtained.

EXAMPLE 196 EXAMPLE 197 5 CHr-Cfl,

and

EXAMPLES 4: AND 5 EXAMPLE 7 I.

25 parts of thedyestufl obtainable according to Ex- 01 CH CH 011 so ample 14 are mixed with 5000 parts of nylon and melted in the normal Way in a nitrogen atmosphere at about N =0 v 285 9 to give a thick liquid mass which is spun into a ON greenish yellow filament. The filament has good fastness g t g V r 3, properties. It can be orientated and/or crimped and V EXAMPLE 15 heat-set to render it shrinkproof. CHrCHrC O O CH, CHZ H: 7 6

EXAMPLE 19s 7 O 25 parts of the dyestufi of the formula CH CH QQQ CH C,

CH: (IX) are mixed with 5000 parts of a condensate of terephthalic acid and glycol or of the dimethyl ester of this acid and V CH3 glycol. The mixture is melted in the normal manner in a CHB'CHFCO 3: I nitrogen atmosphere at about 280. T The thick liquid N 011:0 H mass forms a greenish yellow spun filament which pos- CH3-CHz-COOCH;-G; sesses good fastness properties.

EXAMPLE 24 Having thus disclosed the invention what is claimed is:

EXA] IPLE 199 1. A water-insoluble styryl dyestufi which corresponds 1 part of the dyestufi of the formula to the formula OH CHVCHPO o mom-0 /CN B jag-CH x N GH=C l SOg-eryl CHz-CHa-OOO-CHr-Ca \SO /N CH=C H R1 ON 771 wherein is mixed with 300 parts of polyethylene and spun by the normal extrusion method. Bright greenish yellow fila- 7 R represents a member selected from the group consist ing of chlorine, bromine and the R COO- radical, in which R stands for a member chosen from the class consisting of methyl, "ethyl,,n-propy1,isopropyl,'chloromethyl, methoxymethyl and ethoii ymethyl,

R represents an alkyl radical containing 1 to 4 carbon atoms, when R; stands for a halogen atom as defined above, and represents a member selected from the group consisting of an alkyl radical containing 1 to 4 carbon atoms and the radical 2. A water-insoluble styryl dyestufi which corrmponds to the formula wherein v represents a member selected from the group consisting'of chlorine and the propionoxy radical,

w represents a member selected from the group consisting of hydrogen and the propionoxy'radical, and aryl represents a member selected from the group consisiting of phenyl, halogenatedplienylflower alkylphenyl, naphthyl and tetrahydronaphthyl.

3. The water-insoluble styryl dyestufi which corresponds to the formula L CH! CHa-CHg-G O-CHa-CH; S0r -CHa N CH=O CHrCHrCOO-CHrC 1 CN 12 a V 4. The"water-insolub1e styryl dyestuif which corresponds to the formula 5. The water-insoluble styryl dyestutf which corresponds to the formula om-orn-o o mom-0e CH; 7 Y

/SO2- 1 CH=C\ H our-cure o-o-orn-ol ON 6 The water-insoluble styryl dyestufi which corresponds to the formula 7. The water-insoluble styryl dyestuif which corre- Cl-CHz-CH2 sponds to the formula s0,- -GH| CH=C CHI-C \CN References Cited in the file of this patent UNITED STATES PATENTS Felix et al June 14, 1938 2,120,401 2,226,054 ;Felix et a1 Dec. 24, 1940 2,583,551 'Dickey et'al. Jan. 29, 1952 2,583,614 Taylor Jan. 29, 1952 2,776,310 Straley et al. Jan. 1, 1957 2,850,520

Merian'e t a1. Sept. 2, 1958 

1. A WATER-INSOLUBLE STYRYL DYESTUFF WHICH CORRESPONDS TO THE FORMULA 